Hydrochloric Acid → HCID 70362117, compound

HRID 1165249Notes

Reaction equation

HRID 1165249 reaction equation
[C:1]([OH:8])(=[O:7])[CH2:2][CH2:3][CH2:4][C:5]#[CH:6].[Li]CCCC.CCCCCC.[C:20]1([CH2:26][CH2:27][CH:28]2[CH2:30][O:29]2)[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.Cl>CO.O.CN(P(N(C)C)(N(C)C)=O)C>[OH2:7].[OH:29][CH:28]([CH2:27][CH2:26][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[CH2:30][C:6]#[C:5][CH2:4][CH2:3][CH2:2][C:1]([OH:8])=[O:7]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 1359552-(2-Phenylethyl)oxiraneHCID 1430365-Hexynoic acidHCID 178418339Butyllithium

Product 1

HCID 70362117HCID 70362117, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

In a dry flask under N2 was placed 200 ml of HMPA (distilled over NaH) and 24.4 g (0.218 mole) of 5-hexynoic acid, the product of 1b. The solution was stirred at 0° and was added a solution of n-BuLi in hexane (256 ml, 0.436 mole) dropwise. After 2 hours stirring, 2-phenylethyloxirane (33.9 g. 0.229 mole) was added and stirring was continued at RT for 2 days. The reaction mixture was cooled to 0° and 200 ml of H2O was added. The aqueous solution was acidified with 6N HCl and then extracted with Et2O three times. The ether solution was washed once with H2O and was extracted with aqueous NH4OH solution. The aqueous NH4OH solution was reacidified with 6N HCl and then extracted with ether. Removal of the solvent yielded the crude product. The crude product was converted to the corresponding methyl ester via reaction with MeOH in the presence a catalytic amount of BH3 ·Et2O (0.2 ml). The methyl ester was purified by flash column chromatography (Silica gel, EtOAc-petroleum ether(1:4)) and subsequently was hydrolyzed to the acid in the mixture of K2CO3 -MeOH-H2O at RT. The acid was distilled through a Kugelrohr adaptor to give the title compound, bp 190°-195°/0.01 nmmHg (pot temperature).

Workup

  1. customIn a dry flask under N2 was placed
  2. stirringAfter 2 hours stirring
  3. stirringstirring
  4. temperatureThe reaction mixture was cooled to 0°
  5. extractionextracted with Et2O three times
  6. washThe ether solution was washed once with H2O
  7. extractionwas extracted with aqueous NH4OH solution
  8. extractionextracted with ether
  9. customRemoval of the solvent
  10. customyielded the crude product
  11. customThe methyl ester was purified by flash column chromatography (Silica gel, EtOAc-petroleum ether(1:4))
  12. additionsubsequently was hydrolyzed to the acid in the mixture of K2CO3 -MeOH-H2O at RT
  13. distillationThe acid was distilled through a Kugelrohr adaptor

Sources & evidence

ORD record
ord-4bd2a9e093384120b048aaef96ec36ca
Source dataset
uspto-grants-1990_03
Patent number
US04908384

Reaction notes

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